Liquid-Phase Hydrogenation of Halobenzenes in the Presence of Palladium-Containing Nanodiamonds

Article abstract of DOI:10.1134/S0965544118140049

Abstract: The catalytic activity of palladium-containing nanodiamonds (Pd/ND) is studied in the model reaction of liquid-phase hydrodehalogenation of monohalobenzenes (chlorobenzene, bromobenzene, and iodobenzene) and ortho-, meta-, and para-isomers of dichlorobenzene under mild conditions (Т = 45°С, (Formula presented.)?= 1 atm). The obtained results are compared with the catalytic behavior of the palladium-containing activated carbon (Pd/C) under identical conditions. It is found that catalyst Pd/ND is more active than Pd/C and is more stable against the poisonous effect of hydrogen halide forming during the reaction. Study of the effect of HCl and NaOH additives on the catalyst activity shows that, in the presence of HCl, poisoning of the catalyst occurs: the rate of reaction decreases; in the presence of NaOH, the catalyst activity grows; the rate of reaction increases as a result of hydrogen chloride neutralization by an alkali. For both catalysts the rate of reaction decreases in the sequence Cl > Br > I for monohalobenzenes and in the sequence para- > ortho- > meta-isomer in the case of dichlorobenzenes. The obtained dependences are explained using the quantum-chemical modeling of substrates of model reactions.

Full text of DOI:10.1134/S0965544118140049

ISSN 0965-5441, Petroleum Chemistry, 2018, Vol. 58, No. 14, pp. 1206–1212. © Pleiades Publishing, Ltd., 2018.
Original Russian Text © P.A. Kalmykov, N.A. Magdalinova, M.V. Klyuev, 2018, published in Nanogeterogennyi Kataliz, 2018, Vol. 3, No. 2, pp. 109–115.
Liquid-Phase Hydrogenation of Halobenzenes in the Presence
of Palladium-Containing Nanodiamonds
a,
a
a,
P. A . K al mykov *, N. A. Magdalinova , and M. V. Klyuev **
a
Ivanovo State University, Ivanovo, Russia
*
e-mail: k_p.a@mail.ru
*
*e-mail: klyuev@inbox.ru
Received February 1, 2018
Abstract⎯ The catalytic activity of palladium-containing nanodiamonds (Pd/ND) is studied in the model re-
action of liquid-phase hydrodehalogenation of monohalobenzenes (chlorobenzene, bromobenzene, and io-
dobenzene) and ortho-, meta-, and para-isomers of dichlorobenzene under mild conditions (Т = 45°С,
PH2 = 1 atm). The obtained results are compared with the catalytic behavior of the palladium-containing ac-
tivated carbon (Pd/C) under identical conditions. It is found that catalyst Pd/ND is more active than Pd/C
and is more stable against the poisonous effect of hydrogen halide forming during the reaction. Study of the
effect of HCl and NaOH additives on the catalyst activity shows that, in the presence of HCl, poisoning of
the catalyst occurs: the rate of reaction decreases; in the presence of NaOH, the catalyst activity grows; the
rate of reaction increases as a result of hydrogen chloride neutralization by an alkali. For both catalysts the
rate of reaction decreases in the sequence Cl > Br > I for monohalobenzenes and in the sequence para- > or-
tho- > meta-isomer in the case of dichlorobenzenes. The obtained dependences are explained using the
quantum-chemical modeling of substrates of model reactions.
Keywords: hydrodehalogenation, palladium, catalysts, nanodiamonds, activated carbon, halobenzenes
DOI: 10.1134/S0965544118140049
Halogen-containing organic compounds accumu- ides). The hydrodehalogenation of light aliphatic
lated in the national economy pose a serious threat to halocarbons, including halogenated solvents, more
the environment. Among them, for example, are pes- rarely halobenzenes, is more often conducted in the
ticides (hexachlorobenzene, DDT) and polychlorobi- gas phase [1].
phenyls, which were banned long ago, and environ-
The hydrodehalogenation reaction is frequently
studied using chlorobenzene with a strong С–С1 bond
which is contained in many organic wastes as a model
substrate [1]. Benzene is the main product of chloro-
benzene hydrodehalogenation; however, in some
studies, the presence of diphenyl [12, 13] and chloro-
cyclohexane and cyclohexane [14] in the reaction
mixture was confirmed by analytical methods.
mentally more dangerous polychlorinated dibenzo-p-
dioxins and dibenzofurans, chlorofluorocarbons, and
other chloroorganic solvents (perchloroethylene,
1
,1,1-trichloroethane, carbon tetrachloride, and vinyl
chloride) formed upon their burning [1]. In May 2004,
Russia ratified the Stockholm Convention on Per-
sistent Organic Pollutants, according to which more
than 25000 t of polychlorobiphenyls should be dis-
posed of in our country by 2025 [2]. Among methods
currently applied to dispose of haloorganic com-
pounds (burning, burial (including pumping in deep
layers), irradiation, photochemical and oxidative deg-
radation), catalytic hydrodehalogenation in the pres-
ence of various catalysts, including palladium-con-
taining ones, is the most versatile and ecologically
friendly one [1, 3–14].
This study focuses on the liquid-phase hydrodeha-
logenation of monohalobenzenes (Scheme 1a) and
dichlorobenzenes (Scheme 1b) conducted in the pres-
ence of palladium-containing nanodiamonds
(
Pd/ND) as a catalyst. Owing to their structure nano-
diamonds possess high strength, chemical resistance,
and thermal stability, and the presence of functional
groups facilitates the anchoring of metal clusters with
Catalytic hydrodehalogenation may be carried out a diameter of 5 nm and a thickness of 0.4–1.2 nm [15–
both in the gas and liquid phase either using hydrogen 22]. The obtained results are compared with the data
or via hydrogen transfer from a hydrogen donor (phos- on hydrodehalogenation conducted in the presence of
phorous acid, phosphites, formic acid and its salts, conventional catalyst Pd/C (activated carbon of the
alcohols, metal hydrides, hydrazine hydrate, or alkox- М200 brand).
1206

LIQUID-PHASE HYDROGENATION OF HALOBENZENES
1207
Cl
Cl
H2,cat.
HX
H2,cat.
H2, cat.
−
−HCl
−HCl
X
Cl
X = Cl, Br, I
а)
(
(b)
Scheme 1.
EXPERIMENTAL
Preparation of Catalyst Samples
ν
cD
Φ = R
,
Nanodiamonds containing Pd were synthesized as where R is the average diameter of catalyst particles,
described in [23]. Detonation nanodiamonds with a cm; ν is the rate of reaction, mol/(L s), in the linear
2
portion of the kinetic curve (usually until a 10% con-
version from the theoretically calculated value for each
substrate is reached); c is the substrate concentration,
specific surface area of 307–314 m /g (the average size
of diamond crystalline nucleus composed of ~4-nm
nanodiamond particles united to polycrystals of 100–
–5
2
mol/L; and D is the diffusion coefficient, 10 cm /s.
2
00 nm) and the total content of noncarbon admix-
In the experiments, the Thiele criterion was much
tures not above 0.5 wt % were used. The synthesis was
detailed in [15–20]. Previously, this catalyst was
explored in the hydrogenation and hydroamination of
organic compounds [15–20].
–5
smaller than unity (Ф = 0.1–1.3 × 10 ). This fact pro-
vides unambiguous evidence that the reaction occurs
in the kinetic region.
Investigation Procedures
Hydrodehalogenation Procedure
The content of the catalytically active metal in the
Pd/ND sample was determined by micro-X-ray spec-
tral analysis, and the total specific surface area of the
sample was measured by the BET method according
to nitrogen adsorption using a Quantachrome Nova
Model hydrodehalogenation reactions were run as
follows. Thirty milligrams of the catalyst and 10 mg of
NaBH were loaded in a glass reactor equipped with a
4
temperature-controlled jacket and a magnetic stirrer
(
the rate of stirring was chosen in order to provide
3
200 instrument. The relative error in the determina-
tion of palladium content in the catalyst was not above
10%. X-ray spectral local microanalysis was con-
occurrence of the process in the kinetic region) under
the solvent layer (15 mL), and the content of the reac-
tor was stirred for 10 min. Afterwards, 1 mmol of sub-
strate was added in a hydrogen stream, and hydrode-
±
ducted on a VEGA TS 5130MM digital scanning elec-
tron microscope equipped with detectors of secondary
and reflected electrons of YAG crystals and an energy-
dispersive X-ray microanalyzer equipped with an
INCA Energy2 Si(Li) semiconductor detector. The
results of analysis were computed using the INCA
Energy 200 program and then were recomputed using
the TP3PT software package developed at the Insti-
tute of Experimental Mineralogy, Russian Academy of
Sciences. Analysis was carried out at an accelerating
voltage of 20 kV. The electron current absorbed by the
halogenation was conducted at Т = 45°С and PH2
1
=
atm.
The observed rate of reaction was measured by the
volumetric method according to hydrogen absorption.
It is known that the true catalytic activity of heteroge-
neous catalysts should be reduced to the number of
active sites of the catalyst, whose estimation is hardly
probable. Under identical reaction conditions, the
catalytic activity of the test objects may be compared
–1
in terms of the turnover frequency (TOF, min ), cobalt reference sample was 516–565 pA; by the test
which shows the number of substrate molecules con- sample, 540–620 pA. The size of the electron probe
verted per mole of metal per minute [24]. The error in on the sample surface was 157–200 nm. The amount
the determination of TOF was no greater than 5%.
of titanium and chlorine admixtures was no greater
than 0.3 and 0.1 wt %, respectively. The ash content of
the initial nanodiamonds was not above 2 wt %.
Under the studied conditions, the model reactions
had the zero order with respect to the substrate and the
first order with respect to the catalyst and hydrogen.
The products of the hydrodehalogenation
The occurrence of processes in the kinetic region was reaction were analyzed using a 3700 Series gas chro-
confirmed using the Thiele criterion (Ф) [25]:
matograph equipped with a flame-ionization detector
PETROLEUM CHEMISTRY Vol. 58 No. 14 2018

1208
KALMYKOV et al.
Table 1. Characteristics of halo-organic compounds and activity of catalysts in their hydrodehalogenation reactions
TOF, min–1
PdꢀND PdꢀC
14.6 14.3
Sum of natural
С–Hal Natural charge Natural charge on
charges on carbon Dipole
and halogen moment, D
atoms
Entry
Substrate
bond
length, Å
on halogen
atom
carbon atom
linked to halogen
1
2
3
4
5
6
Chlorobenzene
Bromobenzene
Iodobenzene
1.760
1.918
2.125
–0.026
0.043
0.137
0.009
–0.008
–0.013
–0.026
–0.086
–0.159
–0.061
–0.009
–0.030
–0.052
–0.043
–0.022
–0.052
–0.017
–0.043
2.36
2.39
2.16
3.47
2.22
0
9.8
1.8
6.2
1.9
1.4
1.0
1.9
о-Dichlorobenzene 1.747
m-Dichlorobenzene 1.755
p-Dichlorobenzene 1.755
15.9
8.2
18.4
and a 3 mm × 2000 mm chromatographic glass col- catalyst (Table 1, samples 1–3). As is seen from
umn packed with Lucopren G-1000 (5%) on Chrom- Table 1, the activities of both catalysts are close in this
aton N-AW-DMCS (carrier gas, nitrogen; evapora- reaction. It appears that active sites in PdꢀND and
tion temperature, 80–230°С; column temperature, PdꢀС are distributed on surfaces in such a manner that
4
0–180°С (depending on the analyte); carrier gas flow they are to be equally accessible to monohalobenzene
rate, 1.6 ± 0.02 Lꢀh; and injected sample volume, molecules.
.5–1 μL).
0
In the hydrodehalogenation of dichlorobenzenes,
the activity of both catalysts decreases in the sequence
p-DCB > o-DCB > m-DCB (Table 1, entries 4–6).
Note that the catalytic activity of PdꢀND is an order of
Quantum-Chemical Calculations
These calculations were performed using the magnitude higher than that of the commercial PdꢀC.
NWChem shoftware package [26]. Geometry optimi- This experimental fact may be explained as follows. It
zation and vibrational frequencies were calculated in is known that activated carbon is a porous substance
terms of the functional electron density theory in the having micropores and mesopores on the surface and
B3LYP approximation [27–29] using the correlation- metal particles are anchored predominantly via physi-
consistent split-valence triple-zeta aug-cc-pVTZ basis cal adsorption in these pores. This hampers their
set with the diffuse function. In calculations of an accessibility to the hydrogenated substrates. Nanodia-
iodobenzene molecule, the generated basis set aug-cc- monds, in turn, are polycrystals composed of dia-
pVTZ-pp with relativistic pseudopotential ECP was mond nuclei covered by functional groups which
applied. All calculations were conducted with allow- retain metal particles on the surface. Thus, the active
ance for nonspecific solvation within the framework of sites in PdꢀND are more accessible to substrate mole-
the PCM model in the medium of ethanol (dielectric cules, as evidenced by an increased activity of this cat-
permittivity of the medium, 24.852). The data on the alyst compared to PdꢀС.
distribution of electron density on atoms were derived
According to the liquid-phase chromatography of
within the framework of the natural bond orbital
reaction products, under the test conditions, the
(
NBO) theory incorporated into the NWChem calcu-
hydrogenation of chlorobenzene, bromobenzene, and
dichlorobenzenes over PdꢀND to benzene occurs with
a 100% conversion over 4 to 5 h, whereas the hydrode-
halogenation of o-, m-, and p-dichlorobenzenes over
PdꢀC gives rise to chlorobenzene, which is uninvolved
in further hydrodehalogenation. This finding may
suggest that, after a certain time, the catalyst ceases to
lation package. The visualization of the molecules and
their characteristics was performed using the Chem-
Craft program [30].
RESULTS AND DISCUSSION
The synthesized catalyst PdꢀND has a specific sur- operate apparently because of the poisoning of its
2
face are of 284 m ꢀg, and the size of metal particles is active sites by HCl evolving during the reaction. The
4
–5 nm. Palladium occurs in the zero-valent state formation of HCl was confirmed by qualitative analy-
providing the hydrogenation process.
sis for chloride ion (via reaction with 1% silver nitrate
aqueous solution). The deactivation of palladium cat-
alysts by HCl in hydrodechlorination reactions was
reported in [3–6].
The catalytic properties of PdꢀND were studied in
the liquid-phase hydrodehalogenation of monohalo-
benzenes and dichlorobenzene (DCB) isomers
(
Table 1). In the hydrodehalogenation of monohalo-
An iodide ion is a stronger catalytic poison. As evi-
benzenes, the activity of PdꢀND decreased in the denced by liquid-phase chromatography, in the case of
sequence chlorobenzene > bromobenzene > iodoben- both catalysts, the conversion of iodobenzene is no
zene. A similar dependence was observed for the PdꢀC greater than 10%. The poisonous effect of iodine was
PETROLEUM CHEMISTRY
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LIQUID-PHASE HYDROGENATION OF HALOBENZENES
1209
VH2 , mmol
dehalogenation in the presence of PdꢀC was attained
upon the addition of 2 mmol of NaOH, which not
only neutralized HCl evolving as a result of hydro-
dechlorination but also enriched the surface of palla-
4
3
0
.6
.5
.4
.3
.2
–
dium in electrons via the adsorption of OH ions
0
0
0
0
5
6
exhibiting a strong +M effect and a weak –I effect. As
the amount of NaOH was increased above 2 mmol,
the rate of reaction decreased apparently because of
the effect of salting out on the active sites of the cata-
lysts. In addition, the accumulation of water exerting
the deactivating effect on palladium and the emer-
gence of competitive adsorption with respect to sub-
strate molecules are feasible. Moreover, at high con-
centrations of NaOH, destruction of the support may
take place [4]. For the hydrodehalogenation of chloro-
benzene under the test conditions, the addition of
1
2
0.1
0
2
4
6
8
10
1.5 mmol of NaOH is optimal.
Time, min
When the hydrodehalogenation of dichloroben-
zene isomers is carried out with the addition of 2 mmol
of NaOH, the reaction is completed over 3.5 and 5 h
in the case of PdꢀND and PdꢀС, respectively. For both
catalysts benzene is the single reaction product. Note
that the activity of catalyst PdꢀND grows by 2–
Fig. 1. Initial portions of kinetic curves for p-DCB hydro-
dehalogenation over PdꢀС: (1) without additives,
(
2) 1 mmol of HCl, (3) 1.5 mmol of NaOH, (4) 2 mmol of
NaOH, (5) 2.25 mmol of NaOH, and (6) 3 mmol of
NaOH.
4
times; PdꢀС, by 10–30 times (Fig. 2).
verified experimentally. The model reaction of nitro-
benzene hydrogenation fully stops upon addition of
.1 mol of iodobenzene to the reaction mixture [31].
Figure 3 shows the rate constants of hydrodehalo-
genation over catalyst PdꢀND as a function of the rate
constant over PdꢀС (the numbering of closed cubes on
0
The poisoning of PdꢀC chloride ions by chloride plots corresponds to the numbering of halobenzenes in
ions was proved by adding hydrochloric acid (1 mmol) Table 1). Linear dependences are observed in the
to the reaction mixture. As is clear from Fig. 1, actu- event of both hydrogenolysis of the carbon–halogen
ally upon the addition of НСl, the rate of hydrodeha- bond in monohaloarenes (Fig. 3a) and hydrodehalo-
logenation decreased. НСl evolved in the course of genation of dichlorobenzene isomers in the sequence
reaction was neutralized by adding alkalis, for exam- para- > ortho- > meta-isomer (Fig. 3b). This observa-
ple, NaOH, to the reaction mixture [3, 4]. Study of the tion provides evidence that the mechanism of hydro-
effect of various amounts of NaOH added to bind dehalogenation is preserved with a change in the
chloride ions showed that, when NaOH was added to nature of the palladium support. Furthermore, in the
the reaction mixture, the activity of the catalysts case of hydrodehalogenation of dichlorobenzene iso-
increased (Fig. 1). The highest rate of p-DCB hydro- mers it may be assumed that the mechanism of reac-
TOF, min–1
(а)
TOF, min–1
40
(b)
PdꢀND
PdꢀC
PdꢀND
PdꢀC
20
3
0
0
1
5
2
10
1
0
5
0
0
о-DCB
m-DCB
p-DCB
о-DCB
m-DCB
p-DCB
Fig. 2. Activity of palladium catalysts (TOF, min–1) in the hydrodehalogenation of dichlorobenzene isomers: (a) without NaOH
additive, and (b) upon the addition of 2 mmol of NaOH.
PETROLEUM CHEMISTRY Vol. 58 No. 14 2018

1210
KALMYKOV et al.
k, Lꢀ(mol s)
(а)
k, Lꢀ(mol s)
(b)
PdꢀND
PdꢀND
R = 0.991
R = 0.976
70
60
50
40
30
20
1
10
6
1
1
00
4
9
0
80
2
7
6
5
4
3
2
0
0
0
0
0
0
5
10
3
10
0
10 20 30 40 50 60 70
0
2
4
6
8
10
12
k, Lꢀ(mol s)
k, Lꢀ(mol s)
PdꢀC
PdꢀC
Fig. 3. Relation between rate constants of reactions proceeding over PdꢀND and PdꢀС for the hydrodehalogenation of
a) monohalobenzenes and (b) dichlorobenzene isomers.
(
tion evidently remains invariable with a change in the a partially negatively charged form, and adsorbed
position of the substituent. All correlation points are in molecular hydrogen. On the basis of the above depen-
the confidence interval >95%. It should be noted that dences, it may be assumed that the negative charge on
the rate constants for the hydrogenation of o-DCB the halogen atom should facilitate hydrodehalogena-
and p-DCB have comparable values, whereas the rate tion. Then, in this reaction, a partially positively
constant for the hydrogenation of m-DCB is almost charged form of hydrogen is evidently the active form
two times smaller than these values. Thus, the effect of of hydrogen on the surface of palladium. It is known
concerted (ortho- and para-isomers) and discon- that the longer the bond length, the lower the energy of
certed (meta-isomer) action of substituents (for chlo-
rine both strong +M and –I effects are typical) is
observed, which evidently may affect the efficiency of
the horizontal adsorption of the substrate (the most
preferable for hydrogenation) and the subsequent
hydrodehalogenation process.
its breaking. In our case, the rate of the hydrodehalo-
genation reaction decreases in the sequence Cl > Br >
I, while the length of the C–Hal bond grows in the
opposite direction: Cl < Br < I. At the same time, on
passage from chlorine to iodine, the electronic char-
acter of the halogen atom “softens” and, as a conse-
quence, the C–Hal bond strengthens in the perpen-
dicular adsorption of substrate. Taking into consider-
ation this fact, it may be suggested that during
hydrodehalogenation substrate molecules coordinate
on active sites of the catalyst to form the intermediate
complex “substrate–palladium” in which the car-
bon–halogen bond breaks more easily in the studied
monohalobenzenes in the sequence Cl > Br > I.
In order to gain insight into structure–property
relationships for the tested substrates, quantum-
chemical calculations were performed (Table 1). As
the sequence number of halogen in monohaloben-
zenes grows, the length of the С–Hal bond increases.
The distribution of charges derived in terms of the nat-
ural bond orbitals (NBO) method indicates that a hal-
ogen atom in a chlorobenzene molecule carries a neg-
ative charge. The charge on the halogen increases in
the sequence of substituents Cl < Br < I and its sign
changes to positive beginning from bromobenzene.
For dichlorobenzenes, the value of charge on chlorine
atoms grows in the sequence para- < meta- < оrtho-
isomer.
Figure 5 shows the diagram of highest occupied
molecular orbital (HOMO) and lowest unoccupied
molecular orbital (LUMO) energy distribution for the
tested halobenzenes. A gap between HOMO and
LUMO energies of monohalobenzenes decreases in
the sequence Cl > Br > I. Hence, the rate of hydrode-
halogenation should increase in this sequence. How-
Figure 4 presents the dependence of charge on the
halogen atom on the length of the carbon–halogen ever, as was mentioned above, the rate constant for the
bond in the tested halobenzenes. With increasing tested compounds decreases in the sequence Cl > Br >
length of the carbon–halogen bond and decreasing I for both catalysts. For dichlorobenzene isomers, a
charge on the halogen atom, the rate of the hydrode- gap in HOMO and LUMO energies also decreases in
halogenation reaction declines. In accordance with the direction opposite to an increase in the rate con-
[
32], during the hydrogenation process, several differ- stant of hydrodehalogenation: para- > ortho- > meta-
ent forms of hydrogen may reside on the surface of isomer. It may be expected that, under the studied
palladium, namely, a partially positively charged form, conditions in the hydrodehalogenation of monohalo-
PETROLEUM CHEMISTRY
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2018

LIQUID-PHASE HYDROGENATION OF HALOBENZENES
1211
q(Hal)
.20
the order of 90–100% may be attained over a shorter
time. Thus, hydrodehalogenation under mild condi-
tions in the presence of PdꢀND calls for further
studies.
0
R = 0.941
0.15
3
0.10
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Translated by T. Soboleva
PETROLEUM CHEMISTRY
Vol. 58
No. 14
2018